Polymeric binders for photographic emulsions

ABSTRACT

A photosensitive silver halide emulsion wherein the emulsion binder comprises a graft copolymer of an amine diamide monomer on a polymer containing a plurality of hydroxyl groups.

United States Patent 1 91 Fitzgerald ]March 20, 1973 I POLYMERIC BINDERSFOR 3,396,030 8/1968 Haas ..96/1 14 PHOTOGRAPHIC EMULSIONS 3,408,19910/1968 Saleck etal. "96/114 [75] Inventor: naurice J. Fitzgerald,Canton, FOREIGN PATENTS OR APPLICATIONS ass. I 1,500,666 9/1967 France..96/l14 [73] Asslgnee: Polaroid Corporation, Cambridge, I 9 MassPrimary ExaminerRonald H. Smith [22] Filed: July 6; 1971Attorney-Charles Mikula et a1.

[211 App]. No.: 160,214

[57] ABSTRACT [52 us. c1. ..96/114, 96/84 R A photosensitive silverhalide emulsion h r in h [51] Int. Cl. ..G03c l/04 emulsion binderwmpl'ises a graft copolymer of [58] Field of Search ..96/114 amineiamide monomer n a polymer containing a plurality of hydroxylgroups. 56R f Ct 11 I e erences l e 23 Claims, No Drawings UNITED STATES PATENTS2,409,126 8/1946 Kenyon et a]. ..260/83 POLYMERIC BINDERS FORPHOTOGRAPIIIC EMULSIONS BACKGROUND OF THE INVENTION particular, itsvariable photographic properties and its fixed physical properties, forexample, its diffusion characteristics; much effort has been expended inthe past in order to replace gelatin with a suitable synthetic colloidbinder for photographic silver halide emulsions. Many syntheticpolymeric materials have heretofore been suggested as peptizers forsilver halide emulsions, however, these have generally notfunctionedsatisfactorily and frequently have not fulfilled all of the basicrequirements for a photosensitive silver halide emulsion binder listedfollowing:

1. absent (or constant) photographic activity;

2. ability to form an adsorption layer on microcrystals of silver halidepermitting stable suspensions to be obtained;

3. ability to form adsorption layers as described in (2) above which donot prevent growth 'of silver halide microcrystals during physicalripening; and

4. solubility in water solution.

In addition, hithertofore, much emphasis has been placed on the abilityof the synthetic polymeric material to mix with gelatin, as thisproperty has been critical for employment in partial substitutionreactions with gelatin.'Consequently, many synthetic polymers of theprior art have been materials which allow for the growth of silverhalide crystals only in the presence of gelatin.

A class of synthetic polymers has now been found which is notsusceptible to the deficiencies of the prior I an and which may replacegelatin entirely in photosensitive silver halide emulsions.

Summary of the Invention The present invention is directed to aphotosensitive wherein R R and R each is hydrogen, lower alkyl group,e.g., one to four carbon alkyl group, preferably methyl or ethyl, orhalogen, e.g., chloro, bromo or iodo; R, is hydrogen, lower alkyl,halogen or'cyano; Z is oxygen or nitrogen; R when Z is oxygen, is anelectron pair, and when Z is nitrogen, is hydrogen or lower alkyl, e.g.,one to four carbon alkyl group, preferably methyl or ethyl; R, is alower alkyl or cycloalkyl group, e.g., a one to four carbon alkyl orcycloalkyl group; R, and R each is hydrogen, lower alkyl group or lowercycloalkyl group, e.g., one to four carbons and any combination of R R,,R, and R may be taken together to form a three to seven atom ringstructure; on a polymer containing a plurality of hydroxyl groups. In analternative embodiment, the graft copolymer also includes asecondmonomer grafted thereon, i.e., an ethylenically unsaturated monomer. Instill another embodiment, the above-described polymer comprises only aportion of the binder, the remainder constituting gelatin or a secondsynthetic polymer.

DETAILED DESCRIPTION OF THE INVENTION The present invention is directedto photosensitive silver halide emulsions wherein photosensitive silverhalide crystals are disposed in a synthetic polymeric binder comprisinga polymer containing a plurality of hydroxyl groups having graftedthereon an amine diamide monomer represented by the formula:

fn. it? (111:6

llm

e.g., one to four carbons, and any combination of R R R and R5 may betaken together to form a three to seven atom ring structure.

Such polymers have been found to substantially provide all of the basicrequirements for a gelatin substitute, as delineated above. Theemulsions of the present invention are readily sensitized byconventional sensitizing agents and are characterized by excellentlatent image stability and excellent film speed. In addition, theemulsions of the present invention are much more stable againstdegradation, particularly hydrolysis and the growth of microorganismsthan gelatin.

With regard to the backbone polymer of the graft copolymer; in general,any organic polymer comprising repeating units comprising structuralunits containing a plurality of I groupings capable of being oxidizedby, e.g., a transition metal ion catalyst is useful in the presentinvention. Preferred backbones are substituted or unsubstitutedcellulosic or polyvinyl polymers, and most preferably, a backboneselected from the group consisting of polymeric polyols, polyvinylalcohol, gelatin,

. 3 polysaccharides, partial acetals of polyvinyl alcohol,

etc.

It is believed that upon oxidation of the hydroxyl groups, mention maybe made of the following:

(1) 7 T115611 "6H l a "if Y J H H1011 cellulose 2 """dmbcfigaabi'carboxymethyl cellulose hydroxyethyl cellulose carboxymethylhydroxyethyl cellulose Oll O-GI-IzlICHs H -CHzCHCHa oornonom k y-6phydroxypropyl cellulose methylcellulose dnr-ommc monahydroxypropylmethyl cellulose cinz-o-omono'mcm hydroxybutylmethylcellulose alginic acid COOH OOII

propyleneglycol ,alginate cellulose sulfate kappacarrageenan CIIzOIIOOCHzCHCHa (Illa k ii CH: 8 04H lv Jx l (LE Quinuclidine-3'-y1-2-acrylamido-Z-methylpropionate N-[3 '-(morphol1no)prop-1-yl]-2-acrylam1do-2- methylpropionamide 13) 111: as) CH3 1H3 CH=CH-CONHCC0N11CH:CH2C Hz-N N-on. 0111:0114; O-NH-JJ-C o-Nu-omcn N g I omN-[ 3 -(N "-methylpiperazino )prop-l '-yl]-2-acrylamido-2-methylpropionamide The monomers employed in forming thegraft copolymers suitable for use in the present invention may beprepared by the following general procedure:

N-[2'-(1 -methylpyrrolidin-2"-yl)ethyl]-2-acrylamido-Z-methylpropionamide a9 OH;

0112:011-0 ONH(IJC O-N N-CH;

H R /R7 R1 R2 3 ,1 V y I R: =0 1 N R5 R1 C=0N-[2'-acrylam1do-2'-methy1prop1onyl]-N'-methyl- 1 piperazine J: I

R3- :CH-R R-|C-Ra R1 CZ-RuN (70) CH3 CH3 ll 1 oHFe-c0-NH (:-co-N' 'N4111; 0

Oxazolone Reagent Amine Reagent 1N-[2'-Methacrylamido-2Gmethylpropionyl]-N- The oxazolone reagent may bedissolved in an inert methylpiperazine solvent such as hexane ormethylene chloride and a stoichiometric amount of amine reagent may beadded (71) 0H3 to the solution. The desired monomer crystallizes outCHFCH CO NH 'JJ COCFCHQCHFN of solution in relatively high yield andpurity. The

monomer may be collected by filtration, washed with 3 hexane ormethylene chloride and vacuum dried.

The following table illustrates suitable monomersN-[2'-(2."-acrylamido-2"-methylpropionyloxy)ethyl1 prepared according tothe above-indicated general azatane procedure.

TABLE 1 Elemental analysis 4 Theoretical Foun Reaction M.P., PercentOxazolone reagent Amine reagent solvent Appearance C. yield C II N C H N2-viny1-4-isopropy1-5- N,N-dimethyl ethyl- Hexane White crystals.118-120 oxazolon'e. enediamine. 2-isopropenyl-4-isopropy1-5- .doDlethylethen. ..do.. 117-119 oxazolone. 2-viny1-i4,4dimethyl-5- ..d0IIexane do 76-78 85.0 58.2 9.3 18.5 58.1' 9.4 18.4

oxazo one.

Do fl-(tertiary butylarnino)- Acetone do 157-159 31.0 48.9 7.8 13.2 49.08.1 13.1

' ethanol nitrate. Do fl-(diethylamino)ethanol.. Diethylether. Colorlessoil. 83.0 Do N,N-diothy1-ethyl- Hexane White crystals... 71-72 60.0 61.19.9 16.5 60.8 10.3 16.3 enediamine. 2-vmy.-4-isopropy1-5- do ..d0. .d083-84 oxazolone. 2-vinyl-4,4-dimethyl-5- N,N-dlisopropylethylene-.....do ..d0. 74-75 63.0 63.6 10.3 14.8 63.6 10.5 14.7

oxazolone. diamine.

Do 2-(dimethy1amino)-1 ...do ..do.. 54-55 43.0 59.7 9.6 17.4 59.6 9.717.4 v

aminopropane. Do B-(dimethylaminQ-l- Diethyl ether. Colorless oil 59 59.1 11.6 58 3 9 7 9 2 propane Do 2-pyrrolidinoethylamine. Hexane Whitecrystals... 124-125 92.5 61.6 9.2 16.6 62.0 9.3 16.6 Do2-piperidinoethylamine ..d0. .....d0 131-132 93 5 62.9 9.4 15.7 62 8 9 415 8 Do 3-piperidino-1-aminopro- ..do 1lo 103-104 93 5 64.0 9.7 14. 9 640 9 7 14 6 panc. l)o. 3-morph0lino-l-aminopro- .do. 9697 915 59.4 3.9 Mx 5') 6 9 K 14 1-1 pane.

2-(l-methylpyrr0l1din-2-yl)- ...d0. .....d0........ 912-94 74.0 62.9 9.415.7 62.1; 9.7' 15.6 ethyl amino. Do N-methylpipemzine Diethyletln-r..11o 72-75 62.0 2-isopropeny1-4,4- 1imethyl-5- .do ..do.... .do 115. 964. 0

oxazolone. 2-viny1-4,4-(limethyl-5- 3-(N-methylpiperazino)-1- l1exane.....(lo.. 113-114 95.5 60.8 9.5 18. 9 60.7 9.9 18.5

oxazolone. aminopropnne.

1 Very high boiling point.

CHFCH-COOH (14) acrylic acid methacrylic acid a-chloroacrylic acida-bromoacrylic acid CH CH=CHCOOH 7s crotonic acid CH CH=CH-COOH 79isocrotonic acid B-cliloroacrylic acid BrCH=CH-COOH (81) ,B-bromoacrylicacid B-chloromethacrylic' acid CH =CHCOO-CH;, (as) methyl acrylate CHaethyl methacrylate n-propyl-a chloroacrylate B1'CH=CH-COOCH+CH3)2 (86)isopropyl-B-bromoacrylate isobutyl methacrylate fi-hydroxyethyl acrylate'y-hydroxypropyl acrylate 0112:0-0 00CH2?HCHJ 2-hydroxy-n-propylmethacrylate c11 =cH-c0 N11 (91) acrylamide a-bromoacrylamidemethacrylamide a-ethylacrylamide ClCH=( JCONHa B-chloromethacrylamide2,3-dibromoacrylamide CH CH=CH--CONH (98) crotonamide (nu) CH3 om=cco--Nu-cm N-methylmethacrylamide N,N-dimethylacrylamideN-ethyl-a-chloroacrylamide CH,=CH-CONH-C-(-CH N-tertiary butylacrylamideZ-acrylamidopropionamide 2-methacrylamidopropionamide 2-(a-chloroacrylamido 3-methylbutyramide N-( acetamidomethyl)acrylamideN-(propionamidomethyl)methacrylamide N-( n-butyramidomethyl)a-chloroacrylamide maleic anhydride HOOCCH=CHCOOH maleic acidHOOC-CH=Cl-lCONl-l maleic acid amide HOOC-CH=CH-CO-NHCH CH N-ethylmaleicacid amide N-methyl methylmaleate amide CH =CH-0OCl-l vinylformate CH=CH-OOCCl-l vinyl acetate CH =CH-OH vinyl alcohol isopropenylbromoacetate CH =Cl-IOOCC(-Cl-l vinyl privalate Cl-l -=CHNHCOOC-(-Cl-lN-vinyl-tertiary butylcarbamate ethyl-3-carboxy-3-butenate (lSO) (lSl)fuss) I a-vinylfuran a(-acryloyloxymethyl+tetrahydrofuranp-hydroxystyrene m-hydroxystyrene o-hydroxystyrene p-carboxystyrenem-carboxystyrene N-vinyl-2-pyrrolidone Polymerization of the indicatedmonomers is achieved by conventional transition metal ion catalysttechniques.

The following non-limiting examples illustrate the preparation ofpolymers within the scope of the present invention.

EXAMPLE 1 A flask was charged with 10 ml. of water, 1.06 g. ofacrylamide and 3.40 g. of 2-acrylamidO-Z-methyI-N-[B-(dimethylamino)ethyl]-propionamide.-20 ml. of a 10 percent aqueoussolution of polyvinyl alcohol (Elvanol 70-05, DuPont Company,Wilmington, Delaware) was added to the flask. 1.4 g. of concentratednitric acid was added and nitrogen was bubbled through the solution fortwo hours. The solution was then heated to 55 C.; 0.20 g. of cericammonium nitrate in 2 ml. of water was added and the solution wasstirred for 3 hours. The solution was then cooled, adjusted to a pH of 9with potassium hydroxide and dialyzed for 28 hours against distilledwater. Analysis showed a 1:1:3 graft of acrylamide:Z-acrylamido-2-methyl-N-[B- (dimethylamino)ethyl]-propionamide onpolyvinyl alcohol. 1

EXAMPLE [I A 121:3 graft of acrylamide:Z-acrylamido-Z-methyl-N-[3'-(piperidino)-propyl]-propionamide on polyvinyl alcohol wasprepared according to the procedure of Example I. Y

The following general procedure may be used for preparing photographicemulsions using the graft copolymers of the instant invention as thecolloid binders.

A water-soluble silver salt, such as silver nitrate, may be reacted withat least one water-soluble halide, such as potassium, sodium, orammonium bromide, preferably together with potassium, sodium or ammoniumiodide, in an aqueous solution of the abovedescribed polymer. Theemulsion of silver halide thusformed contains water-soluble salts, as aby-product of the double decomposition reaction in addition to-anyunreacted excess of the initial salts. To remove these solublematerials, the emulsion may be centrifuged and washed with distilledwater to a low conductance. The emulsion may then be redispersed indistilled water. To an aliquot of thisemulsion may be added a knownquantity of a solution of bodying or thickening polymer, such aspolyvinyl alcohol having an average molecular weight of about 100,000(commercially available from E. I. duPont deNemours & Company,Wilmington, Delaware, designated Type 72-60). A surfactant, such asdioctyl ester of sodium sulfosuccinic acid, designated Aerosol OT,(commercially available from American Cyanamid Company, New York, NewYork may be added and the emulsion slot coated onto a base, of cellulosetriacetate sheet 5 mls. thick having a coating of 30 mg./sq. ft. ofhardened gelatin.

Alternatively, the soluble salts may be removed by adding to theemulsion a solution of polyacid such as 1:1 ethylenezmaleic acidcopolymer and lowering the pH to below 5, thereby bringing aboutprecipitation of the polyacid carrying the silver halide grains alongwith the precipitate, and 'then to wash and resuspend the resultingprecipitate by redissolving the polyacid at pH The emulsions may bechemically sensitized with sulfur compounds such as sodium thiosulfateor thiourea, with reducing substances such as stannous chloride; withsalts of noble metals such as gold, rhodium and platinum; with aminesand polyamines; with quaternary ammonium compounds such as alkyla-picolinium bromide; and with polyethylene glycols and derivativesthereof. The emulsions of the present invention require only 5 percentas much gold for chemical sensitization as do gelatin emulsions.

The graft copolymers employed as the binders in the emulsions of thepresent invention may be cross-linked according to conventionalprocedures. As an example, polymers containing amine groups may becross-linked with zirconium salts under alkaline conditions whereinamine-containing polymer is coated with a zirconium salt, for example,zirconium sulfate, and the pH is raised cross-linking the polymer.

Cross-linking agents conventionally employed with ,hydroxyl-containingpolymers, such as boric acid, may 1 also be employed.

sion.

The emulsions of this invention maybe coated and processed according toconventional procedures of the art. They may be coated, for example,onto various types of rigid or flexible supports, such as glass, paper,

metal, and polymeric films of both the synthetic type and those derivedfrom naturally occurring products. As examples of specific materialswhich may serve as supports, mention may be made of paper, aluminum,polymethacrylic acid, methyl and ethyl esters, vinylchloride polymers,polyvinyl acetal, polyamides such as nylon polyesters such as polymericfilm derived from ethylene glycol-terephthalic acid, and cellulosederivatives such as cellulose acetate, triacetate, nitrate, propionate,butyrate, acetate propionate, and acetate butyrate. These novelemulsions of the instant invention have been found to adhere to supportsin a most satisfactory manner.

The polymers employed in the practice of the instant invention maycontain from 5-75 mole percent of the grafted monomer; preferably 20mole percent. The

specific amount employed may be selected by the operator depending uponthe grain particle size and habit desired. For example, the grain sizedistribution of the emulsion may be varied by changing the mole rationand type of monomer grafted on the hydroxyl-containing polymer backbone.

By selecting appropriate monomers to be grafted on thehydroxyl-containing polymers, the instant graft polymers may be made tobe compatible with all water soluble bodying polymers. Emulsions madefrom these novel polymers, may be bodied with any water-solublepolymers, overcoming the disadvantage encountered with gelatin which isonly compatible with a very few polymers in a most limited pH range. Asexamples of specific materials whichmay serve as bodying polymers arepolyvinyl alcohol, polyacrylamide, polyalkylacrylamides, polyvinylpyrrolidone, poly(B-hydroxyethyl acrylate), polyethylene imine andcellulose derivatives such as hydroxypropyl cellulose and methylcellulose. It has been found that using only a small amount of one ormore of the instant polymers, large amounts of photosensitive silverhalide grains may be obtained.

An emulsion made from one of these polymers of the instant invention maytherefore be bodied with a watersoluble polymer such that the polymericconstitution of the resulting emulsion comprises a relatively largepercentage of the bodying polymer.

By selecting appropriate comonomers, copolymers with selected diffusioncharacteristics may be prepared.

The instant polymers containing acidic comonomers may be pH flocculatedin order to remove the soluble salts formed as a byproduct of the doubledecomposition reaction between the water-soluble silver salt and thewater-soluble halide, in addition to any unreacted excess of the initialsalts. As an example, an acid copolymer may be precipitated by loweringthe pH below and then washed and resuspended by raising the pH to above7.

The instant invention will be further illustrated by reference to thefollowing nonlimiting examples in which the preparation of the emulsionwas carried out in the following general manner.

Procedure A A solution of 4.15 g. of the dry graft polymer in 266 ml. ofdistilled water was adjusted to pH 6.30 with dilute nitric acid andmaintained at a temperature of 55 C. To this solution, 44.0 g. of drypotassium bromide and 0.50 g. of dry potassium iodide were added.

A solution of 55 g. of silver nitrate in 500 ml. of distilled water wasprepared. From this silver nitrate solution, 100 ml. was rapidly addedwith continuous agitation to the polymer-halide solution and anadditional 396 ml. was added over a period of 22 minutes. Thereafter,the emulsion was ripened for 30 minutes at 55 C., and then rapidlycooled to below 20 C. Procedure B In an alternative procedure forpreparing the emulsion, the pH of the polymer solution was adjusted to3.0; the amount of dry potassium bromide used was 88.0 g. and the amountof dry potassium iodide used was 1.0 g. In addition, the emulsion wasripened for 60 minutes instead of-for 30 minutes.

The emulsion mixture in both procedures was centrifuged and washed withwater to a low conductance. The emulsion was then redispersed indistilled water. To an aliquot of this emulsion was added a knownquantity of a solution of bodying or thickening polymer of polyvinylalcohol having an average molecular weight of about 100,000(commercially available from E. I. duPont de Nemours & Company,Wilmington, Delaware, designated Type 72-60). A surfactant, such asAerosol OT, was added and the emulsion was slot coated onto a base ofcellulose triacetate sheet 5 mils thick having a coating of 30 mg./sq.ft. of hardened gelatin, (Celfa, commercially available from lnstarSupply Company, New York, New York). This film so prepared was airdried, exposed on a sensitometer, and processed with a processingsolution and an imagereceiving sheet from a Type 107C film assembly(Polaroid Corporation, Cambridge, Massachusetts). The negative andimage-receiving element were maintained in superposed position forseconds, after which they were stripped apart. The photographiccharacteristicsof the resulting positive print were measured on anautomatic recording densitometer.

The following table summarizes silver halide grain sizes obtained inemulsions prepared with polymers of the present invention.

TABLE 2 Grain Size (microns) Range Average Graft copolymer of Example111 0.4-3.0 1.3 Graft copolymer of Example 11 0.5-3.1 1.4

The following table shows densitometer readings obtained on a negativeprepared from an emulsion of the present invention.

TABLE 3 Grain growing polymer 1:]:3-acrylamidez2-acrylamido-2-methyl-N-{B- dimethylaminoethyllpropionamide on polyvinyl alcoholBodying polymer polyvinyl alcohol Polyvinyl alcohol silver ratio 1.0Film base coverage 178.8 mg. Ag/ft. Positive max 1.38 'min 0.50 AD 0.84

in certain photographic applications, it may be desirable to replacepart, but not all, of the gelatin in the photosensitive emulsion. Inview of the characteristics of these polymers described above, andfurther, in view of their compatability with gelatin in substantiallyall proportions, it will be obvious that these polymers are ideallysuited for such work.

The term photosensitive and other terms of similar import are hereinemployed in the generic sense to describe materials possessing physicaland chemical properties which enable them to form usable images whenphotoexposed by radiation.

Since certain changes may be made in the above products and processeswithout departing from the scope of the invention herein involved, it isintended that all matter contained in the above description shall beinterpreted as illustrative only and not in a limiting sense.

What is claimed is:

1. A photosensitive silver halide emulsion wherein the emulsion bindercomprises a graft copolymer of an amine diamide of the formula:

wherein R R and R each are selected from the group graft copolymer.

23 alkyl, lower cycloalkyl, and any combination of R R R, and R, may bechemically joined to form a three to seven atom ring structure, onto apolymer containing a plurality of hydroxyl groups.

5. The product as defined in claim 1 wherein said emulsion includes atleast one chemical sensitizing agent.

6. The product as defined in claim 1 wherein said emulsion includes atleast one optical sensitizing agent.

7. The product as defined in claim 1 wherein said graft copolymerfurther includes a second ethylenically unsaturated monomer grafted ontosaid polymer containing a plurality of hydroxyl groups.

8. The product as defined in claim 7 wherein said amine diamide isdimethylaminoethyl-2-acrylamido-2- methylpropionamide.

9. The product as defined in claim 7 wherein said amide diamide isdimethylaminoethyl-2-acrylamido-3- methylbutyramide.

10. The product as defined in claim 7 wherein said amine diamide isB-(dimethylamino)-ethyl-2'acryalmido-2-methylpropionate.

11. The product as defined in claim 7 wherein said amine diamide is2-acrylamido--2-methyl-N-[2'- (piperidino)-ethyl]-propionamide.

12. The product as defined in claim 7 wherein said second monomer isacrylamide.

13. The product as defined in claim 7 wherein said second monomer isN-isopropylacrylamide.

14. The product as defined in claim 7 wherein said second monomer isacrylamidoacetamide.

15. A method of preparing a photosensitive silver halide emulsion whichcomprises reacting a water-soluble silver salt with a water-solublehalide salt'in an aqueous solution containing a graft copolymer of anamine diamide of the formula:

wherein R R and R each are selected from the group consisting ofhydrogen, lower alkyl and halogen; R, is selected from the groupconsisting of hydrogen, lower alkyl, halogen and cyano; Z is selectedfrom the group consisting of oxygen and nitrogen; when Z is oxygen R isan electron pair and when Z is nitrogen R is selected from the groupconsisting of hydrogen and lower alkyl; R, is selected from the groupconsisting of lower alkyl and lower cycloalkyl groups; R, and R each areselected from the group consisting of hydrogen, lower alkyl, lowercycloalkyl, and any combination of R R R and R may be chemically joinedto form a three to seven atom ring structure, onto a polymer containinga plurality of hydroxyl groups.

16. The method as defined in claim 15 wherein said graft copolymerfurther includes a second ethylenically unsaturated monomer grafted ontoa polymer containing a plurality of hydroxyl groups.

17. The method as defined in claim 16 wherein said amine diamide isdimethylaminoethyl-Z-acrylamido-Z- methylpropionamide.

18. The method as defined in claim 16 wherein said amine diamide isdimethylaminoethyl-Z-acrylamido-3- methylbutyramide. v

19. The methodas defined in claim 16 wherein said amine diamide isB-(dimethylamino)-ethyl-2- acrylamido-2-methylpropionate.

20. The method as defined in claim 16 wherein said amine diamide is2-acrylamido-2-methyl-N-[2'- (piperidino)-ethyl]-propionamide.

21. The method as defined in claim 16 wherein said second monomer isacrylamide.

22. The method as defined in claim 16 wherein said second monomer isN-isopropylacrylamide.

23. The method as defined in claim 16 wherein said second monomer isacrylamidoacetamide.

' :r k a:

2. The product as defined in claim 1 wherein substantially all of saidemulsion binder comprises said graft copolymer.
 3. The product asdefined in claim 1 wherein said graft copolymer comprises 5-75 molepercent of said amine diamide.
 4. The product as defined in claim 1wherein said silver halide emulsion is a silver iodobromide emulsion. 5.The product as defined in claim 1 wherein said emulsion includes atleast one chemical sensitizing agent.
 6. The product as defined in claim1 wherein said emulsion includes at least one optical sensitizing agent.7. The product as defined in claim 1 wherein said graft copolymerfurther includes a second ethylenically unsaturated monomer grafted ontosaid polymer containing a plurality of hydroxyl groups.
 8. The productas defined in claim 7 wherein said amine diamide isdimethylaminoethyl-2-acrylamido-2-methylpropionamide.
 9. The product asdefined in claim 7 wherein said amide diamide isdimethylaminoethyl-2-acrylamido-3-methylbutyramide.
 10. The product asdefined in claim 7 wherein said amine diamide is Beta-(dimethylamino)-ethyl-2-acryalmido-2-methylpropionate.
 11. The productas defined in claim 7 wherein said amine diamide is2-acrylamido-2-methyl-N-(2''-(piperidino)-ethyl)-propionamide.
 12. Theproduct as defined in claim 7 wherein said second monomer is acrylamide.13. The product as defined in claim 7 wherein said second monomer isN-isopropylacrylamide.
 14. The product as defined in claim 7 whereinsaid second monomer is acrylamidoacetamide.
 15. A method of preparing aphotosensitive silver halide emulsion which comprises reacting awater-soluble silver salt with a water-soluble halide salt in an aqueoussolution containing a graft copolymer of an amine diamide of theformula:
 16. The method as defined in claim 15 wherein said graftcopolymer further includes a second ethylenically unsaturated monomergrafted onto a polymer containing a plurality of hydroxyl groups. 17.The method as defined in claim 16 wherein said amine diamide isdimethylaminoethyl-2-acrylamido-2-methylpropionamide.
 18. The method asdefined in claim 16 wherein said amine diamide isdimethylaminoethyl-2-acrylamido-3-methylbutyramide.
 19. The method asdefined in claim 16 wherein said amine diamide is Beta-(dimethylamino)-ethyl-2-acrylamido-2-methylpropionate.
 20. The methodas defined in claim 16 wherein said amine diamide is2-acrylamido-2-methyl-N-(2''-(piperidino)-ethyl)-propionamide.
 21. Themethod as defined in claim 16 wherein said second monomer is acrylamide.22. The method as defined in claim 16 wherein said second monomer isN-isopropylacrylamide.
 23. The method as defined in claim 16 whereinsaid second monomer is acrylamidoacetamide.